Stereoselective Synthesis of Quaternary Amino Acids by Transition Metal Catalyzed Reaction
| Project/Area Number |
17550108
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Tottori University |
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Principal Investigator |
KAWATSURA Motoi Tottori Universityt, Faculty of Engineering, Associate Professor, 工学部, 助教授 (50360243)
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| Project Period (FY) |
2005 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2006: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 2005: ¥2,000,000 (Direct Cost: ¥2,000,000)
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| Keywords | Palladium Catalyst / Allylic Alkylation / Quaternary Amino Acid / Regioselectivity / Diastereoselectivity / Asymmetric Synthesis / Ruthenium Catalyst / Linear Selectivity / アリルアルキル化 / アミノ酸誘導体 |
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| Research Abstract |
In this project, I succeeded to control the regioselectivity and diastereoselectivity in the transition metal catalyzed allylic alkylation of allyl acetates, and achieved to construct chiral quaternary amino acid and its analogues.
I discovered the regio- and diastereo-selectivity in the palladium-catalyzed allylic alkylation of (R)- or (S)-2-acetoxy-4-phenyl-3-butene with N-(diphenylmethylidene)glycinate and N-(diphenylmethylidene)alaninate was highly control by using 2-(diphenylphosphino)benzoic acid. For example, the reaction with N-(diphenylmethylidene)glycinate formed the chiral amino acid analogues which possessing vicinal two chiral tertiary carbon centers at the α and β positions with up to 99% reio- and diastereo-selectivities. The alkylation product was further converted to chiral aspartic acid analogues in 7 steps. I also succeeded to control the regio- and diastereo-selectivity in the reaction with N-(diphenylmethylidene)alaninate, and constructed the amino acid analogues wh
… More
ich possessing vicinal chiral quaternary and tertiary carbon centers at the α and β positions with up to 99% reioselectivity and up to 95% diastereoselectivity. The chiral alkylated product also converted chiral 2,3-dimethylaspartic acid in 7 steps.
Furthermore, I examined the similar stereoselective allylic alkylation with azlactones, and I also succeeded to control the regioselectivity and diastereoselectivity. In the reaction of azlactones, I confirmed the 2-(diphenylphosphino)benzoic acid was again key ligand to control the desired stereoselectivities. For example, the reaction with 2-methyl substituted azlactone proceeded in perfect regioselecitity and 98% diastereoselectivity, and demonstrated to convert it to chiral quaternary aspartic acid analogues. Furthermore, I found the triphenylarsine also an effective ligand for this stereoselective allylic alkylations, and 2-(diphenylphosphino)benzoic acid and triphenylarsine gave different diastereoselectivity.
Totally, I succeeded to control the regio- and diastereo-selectivities in the palladium-catalyzed allylic alkylation of (R)- or (S)-2-acetoxy-4-phenyl-3-butene with several amino acid analogues. The coupling product which possessing vicinal two chiral carbon centers or vicinal chiral quaternary and tertiary carbon centers at the α and β positions were converted chiral quaternary amino acids. Less
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Report
(3 results)
Research Products
(16 results)
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[Journal Article] Ruthenium-catalyzed Linear-selective Allylic Alkylation of Ally Acetates2007
Author(s)
Kawatsura, M., Ata, F., Wada, S., Hayase, S., Uno, H., Itoh, T.
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Journal Title
Chem. Commun. 3
Pages: 298-300
Description
「研究成果報告書概要(和文)」より
Related Report
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[Journal Article] Ruthenium-catalyzed Linear-selective Allylic Alkylation of Allyl Acetates2007
Author(s)
Kawatsura, M., Ata, F., Wada, S., Hayase, S., Uno, H., Itoh, T.
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Journal Title
Chem.Commun.
Pages: 298-300
Description
「研究成果報告書概要(欧文)」より
Related Report
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[Journal Article] Ruthenium-catalyzed Linear-selective Allylic Alkylation of Allyl Acetates2007
Author(s)
Kawatsura, M., Ata, F., Wada, S., Hayase, S., Uno, H., Itoh, T.
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Journal Title
Chem.Commun. 3
Pages: 298-300
Related Report
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[Journal Article] Enhanced Enantioselectivity and Remarkable Acceleration of Lipase-Catalyzed Transesterification Using an Imizadolium PEG-alkyl Sulfate Ionic Liquid2006
Author(s)
Itoh, T., Matsuhita, Y., Abe, Y., Han, S-H., Wada, S., Hayase, S., Kawatsura, M., Takai, S, Morimoto, M., Hirose,Y.
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Journal Title
Chem.Eur.J. 12
Pages: 9228-9237
Related Report
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